Raul Arenal

Boron-nitride and boron-carbonitride nanotubes: synthesis, characterization and theory

We present in this review a joint experimental and theoretical overview of the synthesis techniques and properties of boron-nitride (BN) and boron-carbonitride (BCN) nanotubes. While their tubular structure is similar to that of their carbon analogues, we show that their electronic properties are significantly different. BN tubes are wide band gap insulators while BCN systems can be semiconductors with a band gap in the visible range.

Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D

Single metal atoms and metal clusters have attracted much attention thanks to their advantageous capabilities as heterogeneous catalysts. However, the generation of stable single atoms and clusters on a solid support is still challenging. Herein, we report a new strategy for the generation of single Pt atoms and Pt clusters with exceptionally high thermal stability, formed within purely siliceous MCM-22 during the growth of a two-dimensional zeolite into three dimensions. These subnanometric Pt species are stabilized by MCM-22, even after treatment in air up to 540 °C. Furthermore, these stable Pt species confined within internal framework cavities show size-selective catalysis for the hydrogenation of alkenes. High-temperature oxidation-reduction treatments result in the growth of encapsulated Pt species to small nanoparticles in the approximate size range of 1 to 2 nm. The stability and catalytic activity of encapsulated Pt species is also reflected in the dehydrogenation of propane to propylene.

3D analysis of the morphology and spatial distribution of nitrogen in nitrogen-doped carbon nanotubes by energy-filtered transmission electron microscopy tomography.

We present here the application of the energy-filtered transmission electron microscopy (EFTEM) in the tomographic mode to determine the precise 3D distribution of nitrogen within nitrogen-doped carbon nanotubes (N-CNTs). Several tilt series of energy-filtered images were acquired on the K ionization edges of carbon and nitrogen on a multiwalled N-CNT containing a high amount of nitrogen. Two tilt series of carbon and nitrogen 2D maps were then calculated from the corresponding energy-filtered images by using a proper extraction procedure of the chemical signals. Applying iterative reconstruction algorithms provided two spatially correlated C and N elemental-selective volumes, which were then simultaneously analyzed with the shape-sensitive reconstruction deduced from Zero-Loss recordings. With respect to the previous findings, crucial information obtained by analyzing the 3D chemical maps was that, among the two different kind of arches formed in these nanotubes (transversal or rounded ones depending on their morphology), the transversal arches contain more nitrogen than do the round ones. In addition, a detailed analysis of the shape-sensitive volume allowed the observation of an unexpected change in morphology along the tube axis: close to the round arches (with less N), the tube is roughly cylindrical, whereas near the transversal ones (with more N), its shape changes to a prism. This relatively new technique is very powerful in the material science because it combines the ability of the classical electron tomography to solve 3D structures and the chemical selectivity of the EFTEM imaging.

Atomistic Description of Electron Beam Damage in Nitrogen-Doped Graphene and Single-Walled Carbon Nanotubes

By combining ab initio simulations with state-of-the-art electron microscopy and electron energy loss spectroscopy, we study the mechanism of electron beam damage in nitrogen-doped graphene and carbon nanotubes. Our results show that the incorporation of nitrogen atoms results in noticeable knock-on damage in these structures already at an acceleration voltage of 80 kV, at which essentially no damage is created in pristine structures at corresponding doses. Contrary to an early estimate predicting rapid destruction via sputtering of the nitrogen atoms, in the case of substitutional doping, damage is initiated by displacement of carbon atoms neighboring the nitrogen dopant, leading to the conversion of substitutional dopant sites into pyridinic ones. Although such events are relatively rare at 80 kV, they become significant at higher voltages typically used in electron energy loss spectroscopy studies. Correspondingly, we measured an energy loss spectrum time series at 100 kV that provides direct evidence for such conversions in nitrogen-doped single-walled carbon nanotubes, in excellent agreement with our theoretical prediction. Besides providing an improved understanding of the irradiation stability of these structures, we show that structural changes cannot be neglected in their characterization employing high-energy electrons.

Self-Deactivation of Single-Walled Carbon Nanotube Growth Studied by in Situ Raman Measurements

In situ Raman measurements were used to investigate the kinetics and the self-deactivation of the growth of single-walled carbon nanotubes during catalytic chemical vapor deposition. The kinetics appear controlled by the mass-transport of the gaseous precursor at low precursor pressure and high temperature and by the catalytic decomposition of the precursor at high precursor pressure and low temperature. The initial growth rate and the lifetime display inversely correlated evolutions with the growth parameters. In addition, we measured the activation energy for the healing of defects during the growth and discuss it in comparison to the apparent activation energies measured for the initial growth rate and the lifetime. Our results support that the healing of the edge defects controls both the crystalline order and the growth lifetime.

Processes Controlling the Diameter Distribution of Single-Walled Carbon Nanotubes during Catalytic Chemical Vapor Deposition

Single-walled carbon nanotubes are grown by catalytic chemical vapor deposition in various conditions of temperature and carbon precursor pressure. Systematic analyses of the Raman radial breathing modes at two laser wavelengths are used to monitor the evolution of the diameter distribution. Two distinct domains with opposite influences of the temperature and the precursor pressure on the diameter distribution are evidenced. Thanks to specially designed experiments made of two successive growths, three processes are identified to influence the diameter distribution during the nanotube growth: (i) at too low precursor pressure, nanotube nucleation cannot occur on the smallest catalyst particles; (ii) at low temperature and high precursor pressure, small catalyst particles are preferably encapsulated by disordered carbon structures; (iii) at high temperature, catalyst coarsening causes the disappearance of the smallest catalyst particles.

Experimental evidence of a mechanical coupling between layers in an individual double-walled carbon nanotube.

We perform transmission electron microscopy, electron diffraction, and Raman scattering experiments on an individual suspended double-walled carbon nanotube (DWCNT). The first two techniques allow the unambiguous determination of the DWCNT structure: (12,8)@(16,14). However, the low-frequency features in the Raman spectra cannot be connected to the derived layer diameters d by means of the 1/d power law, widely used for the diameter dependence of the radial-breathing mode of single-walled nanotubes. We discuss this disagreement in terms of mechanical coupling between the layers of the DWCNT, which results in collective vibrational modes. Theoretical predictions for the breathing-like modes of the DWCNT, originating from the radial-breathing modes of the layers, are in a very good agreement with the observed Raman spectra. Moreover, the mechanical coupling qualitatively explains the observation of Raman lines of breathing-like modes, whenever only one of the layers is in resonance with the laser energy.

Atomic Configuration of Nitrogen-Doped Single-Walled Carbon Nanotubes

Having access to the chemical environment at the atomic level of a dopant in a nanostructure is crucial for the understanding of its properties. We have performed atomically resolved electron energy-loss spectroscopy to detect individual nitrogen dopants in single-walled carbon nanotubes and compared with first-principles calculations. We demonstrate that nitrogen doping occurs as single atoms in different bonding configurations: graphitic-like and pyrrolic-like substitutional nitrogen neighboring local lattice distortion such as Stone-Thrower-Wales defects. We also show that the largest fraction of nitrogen amount is found in poly aromatic species that are adsorbed on the surface of the nanotube walls. The stability under the electron beam of these nanotubes has been studied in two different cases of nitrogen incorporation content and configuration. These findings provide key information for the applications of these nanostructures.

SERS Detection of Amyloid Oligomers on Metallorganic-Decorated Plasmonic Beads

Protein misfolded proteins are among the most toxic endogenous species of macromolecules. These chemical entities are responsible for neurodegenerative disorders such as Alzheimers, Parkinsons, Creutzfeldt-Jakobs and different non-neurophatic amyloidosis. Notably, these oligomers show a combination of marked heterogeneity and low abundance in body fluids, which have prevented a reliable detection by immunological methods so far. Herein we exploit the selectivity of proteins to react with metallic ions and the sensitivity of surface-enhanced Raman spectroscopy (SERS) toward small electronic changes in coordination compounds to design and engineer a reliable optical sensor for protein misfolded oligomers. Our strategy relies on the functionalization of Au nanoparticle-decorated polystyrene beads with an effective metallorganic Raman chemoreceptor, composed by Al(3+) ions coordinated to 4-mercaptobenzoic acid (MBA) with high Raman cross-section, that selectively binds aberrant protein oligomers. The mechanical deformations of the MBA phenyl ring upon complexation with the oligomeric species are registered in its SERS spectrum and can be quantitatively correlated with the concentration of the target biomolecule. The SERS platform used here appears promising for future implementation of diagnostic tools of aberrant species associated with protein deposition diseases, including those with a strong social and economic impact, such as Alzheimers and Parkinsons diseases.

EEL spectroscopic tomography: Towards a new dimension in nanomaterials analysis

Electron tomography is a widely spread technique for recovering the three dimensional (3D) shape of nanostructured materials. Using a spectroscopic signal to achieve a reconstruction adds a fourth chemical dimension to the 3D structure. Up to date, energy filtering of the images in the transmission electron microscope (EFTEM) is the usual spectroscopic method even if most of the information in the spectrum is lost. Unlike EFTEM tomography, the use of electron energy-loss spectroscopy (EELS) spectrum images (SI) for tomographic reconstruction retains all chemical information, and the possibilities of this new approach still remain to be fully exploited. In this article we prove the feasibility of EEL spectroscopic tomography at low voltages (80 kV) and short acquisition times from data acquired using an aberration corrected instrument and data treatment by Multivariate Analysis (MVA), applied to Fe(x)Co((3-x))O(4)@Co(3)O(4) mesoporous materials. This approach provides a new scope into materials; the recovery of full EELS signal in 3D.